CN109796421A - A kind of acrylate and its synthetic method, coating - Google Patents
A kind of acrylate and its synthetic method, coating Download PDFInfo
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- CN109796421A CN109796421A CN201711143931.7A CN201711143931A CN109796421A CN 109796421 A CN109796421 A CN 109796421A CN 201711143931 A CN201711143931 A CN 201711143931A CN 109796421 A CN109796421 A CN 109796421A
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Abstract
The invention discloses a kind of acrylate and its synthetic methods, coating, belong to organic synthesis field.The synthetic method includes: that molar ratio is added into reactor is (2~4): 1 6-caprolactone, trihydroxyethyl isocyanuric ester form the first mixed system；Under nitrogen atmosphere, the first mixed system is heated to 100 DEG C~180 DEG C, the first catalyst is added into the first mixed system, carried out the first reaction, obtain trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester；After reaction to first, it is added into reactor with trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester solvent identical in quality, is (2~4): 1 acrylic acid with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, form the second mixed system；At 80 DEG C~120 DEG C, the second catalyst is added into the second mixed system, carries out the second reaction, obtains acrylate.Synthetic method provided by the invention can prepare the fast acrylate of water-tolerant, curing rate.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of acrylate and its synthetic method, coating.
Background technique
Trihydroxyethyl isocyanuric triacrylate, due to good water resistance, chemical-resistance and hardness
Big feature is typically used as the raw material of curing agent, hydrophobing agent.However trihydroxyethyl isocyanuric triacrylate is at normal temperature
Viscosity it is very big, and it can be crystallized at low temperature, be unfavorable for the application of product.In view of hydroxyethyl isocyanurate triacrylate
It is a kind of trifunctional acrylate as made of trihydroxyethyl isocyanuric ester and acroleic acid esterification, and the property of acrylate is past
It is past to be determined by its structure.Therefore, it is necessary to provide a kind of acrylic acid different from hydroxyethyl isocyanurate triacrylate structure
Ester, it is the problems of above-mentioned to solve trihydroxyethyl isocyanuric triacrylate
The prior art provides a kind of acrylate, the acrylate be by modified trihydroxyethyl isocyanuric ester with
Acrylic acid is prepared by reaction.Wherein, trihydroxyethyl isocyanuric ester is modified using ethylene oxide, makes itself and epoxy
Ethane occur ethoxylation, generate polyethers intermediate product, and the polyethers intermediate product can react with acrylic acid generate this third
Olefin(e) acid ester.
The inventor finds that the existing technology has at least the following problems:
Compared with trihydroxyethyl isocyanuric triacrylate, the water resistance for the acrylate that the prior art provides is significantly
Decline, and curing rate and hardness are also declined.
Summary of the invention
The embodiment of the invention provides a kind of acrylate and its synthetic methods, coating, to solve the above problems.The skill
Art scheme is as follows:
In a first aspect, providing a kind of synthetic method of acrylate, the synthetic method includes:
It is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanuric ester form first
Mixed system, and remove the moisture in first mixed system；
Under nitrogen atmosphere, first mixed system is heated to 100 DEG C~180 DEG C, and to first mixture
The first catalyst is added in system, carries out the first reaction, obtains trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester；Described
The quality of one catalyst is the 0.01%~2% of first mixed system and the first catalyst gross mass；
After reaction to described first, it is sequentially added in Xiang Suoshu reactor and the 3 (6- of trihydroxyethyl isocyanuric
Hydroxyl 1- caproic acid) ester solvent identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (the 6- hydroxyl 1- caproic acid) ester be
(2~4): 1 acrylic acid forms the second mixed system；
At 80 DEG C~120 DEG C, the second catalyst is added in the second mixed system of Xiang Suoshu, carries out the second reaction, obtains
Acrylate；The quality of second catalyst is the 0.5% of second mixed system and the second catalyst gross mass
~5%.
In a kind of possible design, the molar ratio of the 6-caprolactone and the trihydroxyethyl isocyanuric ester is (2.5
~3.5): 1.
A kind of moisture in possible design, in the first mixed system of the removal, comprising:
First mixed system is heated to 80 DEG C~110 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracted out
Moisture in first mixed system, until the quality of the moisture is less than the 0.05% of the first mixed system quality.
It is defeated in Xiang Suoshu reactor after removing the moisture in first mixed system in a kind of possible design
The nitrogen for sending flow to be at least 0.1L/min, so that first mixed system is in the nitrogen atmosphere.
In a kind of possible design, the quality of first catalyst is that first mixed system is urged with described first
The 0.05%~1% of agent gross mass.
In a kind of possible design, first catalyst is stannous octoate, dibutyl tin dilaurate, n-butanol
At least one of zirconium, bismuth neodecanoate.
In a kind of possible design, after first mixed system is heated to 130 DEG C~140 DEG C, to the reaction
First catalyst is added in device.
In a kind of possible design, in carrying out first reaction process, the ε-is obtained using gas chromatography
Mass fraction of the caprolactone in the reactor determines first reaction if the mass fraction is equal to or less than 5%
Terminate.
In a kind of possible design, the solvent is toluene.
In a kind of possible design, the acrylic acid and trihydroxyethyl isocyanuric 3 (the 6- hydroxyl 1- caproic acid) ester
Molar ratio be (2.7~3.7): 1.
In a kind of possible design, second catalyst is methane sulfonic acid, in p-methyl benzenesulfonic acid, trifluoromethane sulfonic acid
At least one.
In a kind of possible design, the quality of second catalyst is that second mixed system is urged with described second
The 1%~4% of agent gross mass.
In a kind of possible design, after sequentially adding the solvent, the acrylic acid into the reactor, and
At 90 DEG C~110 DEG C, second catalyst is added in Xiang Suoshu reactor, carries out second reaction.
Second aspect provides a kind of acrylate, is prepared using synthetic method described in first aspect, and described third
The chemical structural formula of olefin(e) acid ester is as follows:
The third aspect provides a kind of coating, which includes acrylate described in second aspect.
Technical solution provided in an embodiment of the present invention has the benefit that
Synthetic method provided in an embodiment of the present invention by being first modified to trihydroxyethyl isocyanuric ester, and utilizes
Modified trihydroxyethyl isocyanuric ester and acrylic acid carry out esterification, can be prepared that water resistance is good, solidification speed
The acrylate that degree is fast and hardness is big, can solve the problems of prior art, be conducive to the application of product.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention is made below further
Ground detailed description.
In a first aspect, the embodiment of the invention provides a kind of synthetic method of acrylate, which includes:
Step 101, molar ratio is added into reactor is (2~4): 1 6-caprolactone, trihydroxyethyl isocyanuric ester,
The first mixed system is formed, and removes the moisture in the first mixed system.
Step 102, under nitrogen atmosphere, is heated to 100 DEG C~180 DEG C for the first mixed system, and into mixed system
The first catalyst is added, carries out the first reaction, obtains trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester；First catalyst
Quality be the 0.01%~2% of the first mixed system and the first catalyst gross mass.
Step 103, to first after reaction, sequentially added into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) ester solvent identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester be (2~4): 1
Acrylic acid, formed the second mixed system.
Step 104, at 80 DEG C~120 DEG C, be added the second catalyst into the second mixed system, carry out the second reaction,
Obtain acrylate；The quality of second catalyst is the 0.5%~5% of the second mixed system and the second catalyst gross mass.
Wherein, the chemical formula structure formula of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is as follows:
It can be seen that from the chemical formula structure formula of above-mentioned trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester due to not changing
Property 3 groups of trihydroxyethyl isocyanuric ester be to be arranged around intermediate cyclic structure, certain steric hindrance can be generated, and
Each hydroxyl of modified trihydroxyethyl isocyanuric ester is connected with the ε -6-caprolactone for having opened ring, that is, is connected to one
It is a to reduce steric hindrance with free-moving segment, the curing rate of modified trihydroxyethyl isocyanuric ester is improved, into
And also improve the curing rate of the esterification products of (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid；And by
In (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 be polyester type organic, therefore (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) product after ester and acroleic acid esterification is also polyester type organic, and polyester type organic and polyethers type organic (example
Such as, is produced from the polyethers centre that prior art ethylene oxide and trihydroxyethyl isocyanuric ester carry out ethoxylation and generate
Object) it compares, water resistance is stronger；Contain polyester additionally, due to the modified trihydroxyethyl isocyanuric ester of institute of the embodiment of the present invention
Segment, and the hardness of polyester segment be greater than the prior art polyether segment in modified trihydroxyethyl isocyanuric ester it is hard
Degree, then when the embodiment of the present invention the esterification products of modified trihydroxyethyl isocyanuric ester and acrylic acid also contain polyester
Segment, therefore the lesser defect of provided acrylate hardness in the prior art can be overcome.Therefore, the embodiment of the present invention passes through
6-caprolactone is added into trihydroxyethyl isocyanuric ester, and the two is made to react, it can be to trihydroxyethyl isocyanuric ester
It is modified.
As it can be seen that synthetic method provided in an embodiment of the present invention, by being first modified to trihydroxyethyl isocyanuric ester, and
Using the esterification of modified trihydroxyethyl isocyanuric ester and acrylic acid, it can be prepared that water resistance is good, solidification speed
The acrylate that degree is fast and hardness is big, can solve the problems of prior art, be conducive to the application of product.
Each step of synthetic method provided in an embodiment of the present invention is illustrated below:
In a step 101, it is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanide urine
Acid esters forms the first mixed system, and removes the moisture in the first mixed system.
It is effectively modified in order to be carried out to trihydroxyethyl isocyanuric ester, need to guarantee the every of trihydroxyethyl isocyanuric ester
All connect a 6-caprolactone on a hydroxyl, and the additional amount of 6-caprolactone and trihydroxyethyl isocyanuric ester, 6-caprolactone
Purity influence the modified effect to trihydroxyethyl isocyanuric ester.
In terms of the additional amount of 6-caprolactone, the modified effect of trihydroxyethyl isocyanuric ester can be described as: when
When the additional amount of 6-caprolactone is too low, hydroxyl a part of in trihydroxyethyl isocyanuric ester can be prevented from connecting 6-caprolactone,
Also the hydroxyl of the part cannot be modified, and then weakens the modified effect to trihydroxyethyl isocyanuric ester；And work as ε-
When the additional amount of caprolactone is too high, a part of hydroxyl connection 2 or more in trihydroxyethyl isocyanuric ester 6-caprolactones can be made,
The double bond density of acrylate after will lead to (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acroleic acid esterification declines
Amplitude is excessive, and then influences the curing rate of acrylate.
Based on above-mentioned, in order to improve 6-caprolactone to the modified effect and above-mentioned acrylic acid of trihydroxyethyl isocyanuric ester
The curing rate of ester, in the embodiment of the present invention, the molar ratio of 6-caprolactone and trihydroxyethyl isocyanuric ester may be configured as (2.5
~3.5): 1, for example, the molar ratio can be set to 2.5:1,2.6:1,2.7:1,2.8:1,2.9:1,3.0:1,3.1:
1,3.2:1,3.3:1,3.4:1,3.5:1 etc..
About trihydroxyethyl isocyanuric ester, 6-caprolactone purity in terms of, in order to ensure trihydroxyethyl isocyanuric ester
Each hydroxyl be connected with 6-caprolactone, it is pure that the purity of trihydroxyethyl isocyanuric ester and 6-caprolactone may be configured as chemistry.
Since 6-caprolactone is aqueous solution, the embodiment of the present invention imitates the modified of trihydroxyethyl isocyanuric ester to improve
Fruit, and remove trihydroxyethyl isocyanuric ester and be formed by the moisture of the first mixed system with 6-caprolactone.Wherein, 6-caprolactone
For undeformed prototype structure.
When implementing, can be added through vacuum pumping method or into mixed system the method for water absorbing agent (such as molecular sieve) come
Remove the moisture in the first mixed system.The moisture in the first mixed system is removed according to the latter's method, is not only needed a large amount of
Water absorbing agent, but also need filtration step, which increase processing costs and processing time.Therefore, the embodiment of the present invention uses
The method vacuumized removes the moisture in the first mixed system, this method are as follows: the first mixed system is heated to 80 DEG C~110
DEG C, and in the case where vacuum degree is at least -0.095MPa, the moisture in the first mixed system is extracted out, until the quality of moisture is less than
0.05%.
Specifically, the first mixed system is first heated to 80 DEG C~110 DEG C, make the moisture evaporation in the first mixed system；
Then, the air in abstraction reaction device, until the vacuum degree in reactor is at least -0.095MPa；It later will be in reactor
Air pressure maintains -0.095MPa or more, and extracts the moisture in the first mixed system, until the quality of moisture is less than the first mixing
The 0.05% of system gross mass, such as 0.04%, 0.03%, 0.02%, 0.01% etc..
Wherein, the volume and extraction dynamics of the time and the first mixed system extracted to the first mixed system have
Close, for example, the time that the embodiment of the present invention extracts the first mixed system is at least 2 hours, for example, 2 hours, 3 hours,
4 hours etc..
It should be noted that vacuum degree is more negative, value is bigger, for example, vacuum degree -0.095MPa is greater than vacuum degree -
0.085MPa。
In a step 102, under nitrogen atmosphere, the first mixed system is heated to 100 DEG C~180 DEG C, and mixed to first
The first catalyst is added in zoarium system, carries out the first reaction, obtains trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester,
In, the quality of the first catalyst is the 0.01%~2% of the first mixed system and catalyst gross mass.
In the esterification process of trihydroxyethyl isocyanuric ester and 6-caprolactone, oxygen can occur for trihydroxyethyl isocyanuric ester
Change reaction, and then weakens the modified effect to trihydroxyethyl isocyanuric ester.For this problem, the embodiment of the present invention is by three hydroxyl second
Base chlorinated isocyanurates and 6-caprolactone carry out esterification in nitrogen atmosphere.When implementing, when in the first mixed system of removal
Moisture after, feed flow can be at least 0.1L/min into reactor and (for example, may be configured as 0.1L/min, 0.2L/
Min, 0.3L/min, 0.4L/min, 0.5L/min etc.) nitrogen so that the first mixed system is in nitrogen atmosphere.
Wherein, the reaction temperature in the step, the type of the first catalyst and additional amount urinate trihydroxyethyl isocyanide
The modified effect of acid esters has an impact, and is illustrated one by one to above three factor below.
In terms of reaction temperature, since the fusing point of trihydroxyethyl isocyanuric ester is 130 DEG C, at 130 DEG C hereinafter, three hydroxyls
With 6-caprolactone out-phase reaction can occur for ethyl chlorinated isocyanurates, be unfavorable for the progress of the first reaction.If at this point, to three hydroxyl second
The first catalyst is added in base chlorinated isocyanurates, will lead to a part of hydroxyl of trihydroxyethyl isocyanuric ester and do not react, and
Excessive 6-caprolactone has been gone up in connection on the alkyl of another part trihydroxyethyl isocyanuric ester, and then it is different to will lead to trihydroxyethyl
Cyanurate and the acrylate component after acroleic acid esterification are uneven；And due to containing in the acrylate there are many ester bond,
So that the acrylate easily turns yellow under 140 DEG C of high temperature, the application of the acrylate, such as answering in varnish field will affect
With.
It (for example, can be set in this regard, the first mixed system is heated to 130 DEG C~140 DEG C by the embodiment of the present invention
130 DEG C, 132 DEG C, 134 DEG C, 136 DEG C, 138 DEG C, 140 DEG C etc.) after, the first catalyst is added into reactor.
In terms of catalyst charge, when the first catalyst charge is too low, it is unfavorable for the progress of the first reaction, meeting
Extend the reaction time, and then leads to the colour changed into yellow of the first mixed system and reaction product；And when the first catalyst charge mistake
Gao Shi can generate by-product, reduce to three hydroxyls since the active difference of 3 hydroxyls of trihydroxyethyl isocyanuric ester is little
The modified effect of ethyl chlorinated isocyanurates.
To solve the above-mentioned problems, the quality of the first catalyst in the embodiment of the present invention may be configured as the first mixed system
With the 0.05%~1% of the first catalyst gross mass, for example, may be configured as 0.05%, 0.06%, 0.07%, 0.08%,
0.09%, 0.1% etc..
In terms of the type of catalyst, for being catalyzed trihydroxyethyl isocyanuric ester and 6-caprolactone reacts the
The type of one catalyst can be set to it is a variety of, as long as the open loop of 6-caprolactone can be promoted.For example, the present invention is implemented
The first catalyst in example can be at least one of stannous octoate, dibutyl tin dilaurate, zirconium-n-butylate, bismuth neodecanoate.
Since the content of 6-caprolactone will affect (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acroleic acid esterification
The performance of acrylate afterwards, such as mechanical performance.For this problem, the embodiment of the present invention is carrying out the first reaction process
In, 6-caprolactone mass fraction in the reactor is obtained using gas chromatography, if the mass fraction of 6-caprolactone be equal to or
When less than 5%, determine that the first reaction terminates.
It should be noted that the mass fraction of 6-caprolactone in the reactor, the also referred to as mass fraction of 6-caprolactone, refer to
It is the ratio of mixture gross mass in the quality and reactor of 6-caprolactone.Wherein, the mixture in reactor includes three hydroxyl second
Base chlorinated isocyanurates, 6-caprolactone and the first catalyst.
Specifically: it is carried out in the first reaction process in trihydroxyethyl isocyanuric ester and 6-caprolactone, at predetermined time intervals
(for example, 5min, 6min, 7min etc.) takes out the mixture in reactor, and detects the mixture using gas chromatograph
The mass fraction of middle 6-caprolactone；When the mass fraction of 6-caprolactone is equal to or less than 5%, it is believed that the first reaction terminates.This
When, stop heating to the first mixed system.
It should be noted that when trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester temperature be reduced to 60 DEG C hereinafter,
Can discharge preservation, and when acrylate to be synthesized further takes out；Step 103 can also directly be carried out.
Wherein, gas chromatography is used to carry out measurement of species concentrations to be known in the art.Since trihydroxyethyl isocyanide is urinated
The boiling point of sour 3 (6- hydroxyl 1- caproic acid) esters is higher, so the embodiment of the present invention obtains the quality of 6-caprolactone with the following method
Score: the standard curve of 6-caprolactone in said mixture is first obtained (i.e. on the standard curve first with the method for headspace sampling
The corresponding 6-caprolactone of a point mass fraction), then using headspace injection method to 6-caprolactone in said mixture
Quality surveyed, and bring measured result into mass fraction that standard curve converses 6-caprolactone.
In step 103, after reaction to first, it is sequentially added into reactor and 3 (6- of trihydroxyethyl isocyanuric
Hydroxyl 1- caproic acid) ester solvent identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester be (2~
4): 1 acrylic acid forms the second mixed system.
Wherein, it is toluene that the solvent in the step, which can be set to the solvent in multiple types, such as the embodiment of the present invention, because
There is suitable boiling point and good band water efficiency for toluene.
When the additional amount of acrylic acid is very little, the trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) of a part will lead to
Ester loses reactivity, and then can reduce the double bond density of acrylate；And when the additional amount of acrylic acid is excessive, propylene can be led
The waste of acid.To solve the above-mentioned problems, in the embodiment of the present invention, acrylic acid and trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- oneself
Acid) ester molar ratio be (2.7~3.7): 1, for example, the molar ratio may be configured as 2.7:1,2.9:1,3.1:1,3.3:1,
3.5:1,3.7:1 etc..
At step 104, at 80 DEG C~120 DEG C, the second catalyst is added into the second mixed system, it is anti-to carry out second
It answers, obtains acrylate；Wherein, the quality of the second catalyst is the 0.5% of the second mixed system and the second catalyst gross mass
~5%.
The type and additional amount of reaction temperature, the second catalyst in the step have shadow to the generation of acrylate
It rings, above three factor is illustrated one by one below.
In terms of reaction temperature, when the reaction temperature is too low, the flow velocity of the mixture in reactor is very slow, leads to second
The reaction time of reaction is too long, and then will affect the color of acrylate；And when the reaction temperature is too high, the mixing in reactor
Object can generate double bond, increase its cured risk.In this regard, sequentially adding solvent, third into reactor in the embodiment of the present invention
After olefin(e) acid, and under 90 DEG C~110 DEG C (for example, it can be provided 90 DEG C, 100 DEG C, 110 DEG C etc.), add into reactor
Enter the second catalyst, carries out the second reaction.
In terms of the second catalyst charge, when the second catalyst charge is too low, be unfavorable for the first reaction into
Row, can extend the reaction time, and then lead to the colour changed into yellow of acrylate；And when the second catalyst charge is excessively high, it can send out
Raw some side reactions, influence the quality of acrylate.
To solve the above-mentioned problems, the quality of the second catalyst in the embodiment of the present invention may be configured as the second mixed system
With the 1%~4% of the second catalyst gross mass, for example, may be configured as 1%, 2%, 3%, 4% etc..
In terms of the type of the second catalyst, for be catalyzed (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 with
The type for the second catalyst that acrylic acid reacts can be set to a variety of, for example, second in the embodiment of the present invention urges
Agent is at least one of methane sulfonic acid, p-methyl benzenesulfonic acid, trifluoromethane sulfonic acid.
In order to avoid carrying out long-time heating to acrylate, and its performance is influenced, the embodiment of the present invention uses efficient liquid
The extent of reaction of the second reaction of phase chromatography detection, when (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid
When gross mass is the 85%~100% of the preceding the two gross mass of reaction, it is believed that the second reaction terminates, and stops heating at this time.
Specifically: it is carried out in the second reaction process in (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid,
(for example, 5min, 6min, 7min etc.) takes out the mixture in reactor at predetermined time intervals, and utilizes high-efficient liquid phase color
Spectrometer detects the mass fraction of trihydroxyethyl isocyanuric 3 in the mixture (6- hydroxyl 1- caproic acid) ester and acrylic acid, later
Gross mass both in reactor out；When the gross mass of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester and acrylic acid
For react before both gross mass 0%~15% when, it is believed that second reaction terminate, at this time stop heating.
Wherein, using high performance liquid chromatography detection content of material be it is known in the art, that is, utilize high-efficient liquid phase color
Spectrometer can detect the mass fraction of each ingredient in mixed solution.
After reaction second, in order to extract reaction product, i.e. acrylate from reactor, the embodiment of the present invention can
Lye (such as sodium hydroxide) removal excessive propene acid and the second catalyst are added in the reactor；Later, it is gone using the way of distillation
Except solvent (such as toluene), after the quality of solvent is equal to or less than the 10% of acrylate and solvent gross mass, stripping is used
Tower removes remaining solvent, to obtain the acrylate of high-purity.
Second aspect, the embodiment of the invention provides a kind of acrylate, utilize synthetic method system described in first aspect
Standby to obtain, the chemical structural formula of the acrylate is as follows:
The acrylate of above structure is by the modified trihydroxyethyl isocyanuric ester of first aspect and acroleic acid esterification
Obtain, therefore acrylate provided in an embodiment of the present invention not only has a good water resistance, and its curing rate fastly with
And hardness is big, can solve the problems of prior art, is conducive to the application of product.
The third aspect, the embodiment of the invention also provides a kind of coating, which includes acrylic acid described in second aspect
Ester.
Acrylate provided in an embodiment of the present invention not only has a good water resistance, and its curing rate it is fast and
Hardness is big, can solve the problems of prior art, is conducive to it in coating, especially in polyurethane ultraviolet curing coating
Using.
All the above alternatives can form the alternative embodiment of the disclosure, herein no longer using any combination
It repeats one by one.
Hereinafter the present invention will be further described through by specific embodiment.
In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer
It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.
Wherein, trihydroxyethyl isocyanuric ester is purchased from Yangzhou Suntory Ltd., and 6-caprolactone is purchased from Japanese big respectively
Sai Lu plastics Co., Ltd, toluene, acrylic acid, stannous octoate, di lauric dibutyl, zirconium-n-butylate, bismuth neodecanoate, methyl sulphur
Acid, p-methyl benzenesulfonic acid, trifluoromethane sulfonic acid are purchased from Aladdin reagent Co., Ltd.
Embodiment 1
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.6:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 135 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
The dibutyl tin dilaurate (as the first catalyst) of agent gross mass 1.5%, is reacted.During the reaction, it uses
Gas chromatography judges reaction end, when the mass fraction of 6-caprolactone is 3%, it is believed that reaction terminates；Reaction product is dropped
Temperature is to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 2
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.6:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 120 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
2% zirconium-n-butylate (as the first catalyst) of agent gross mass, is reacted.During the reaction, using gas-chromatography
Method judges reaction end, when the mass fraction of 6-caprolactone is 2%, it is believed that reaction terminates；And reaction product is cooled to 60
DEG C hereinafter, discharging save, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 3
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 3.3:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 170 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
0.3% stannous octoate catalyst (as the first catalyst) of agent gross mass, is reacted.During the reaction, it uses
Gas chromatography judges reaction end, when the mass fraction of 6-caprolactone is 3.5%, it is believed that reaction terminates；And reaction is produced
Object cools to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 4
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
Be added into reactor molar ratio be the 6-caprolactone of 3.5:1, trihydroxyethyl isocyanuric ester, form first
Mixed system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixture
Moisture in system, wherein extracting the time is 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that first is mixed
Zoarium system is in nitrogen atmosphere.First mixed system is heated to 180 DEG C, and it is the first mixed system and first that quality, which is added,
2% bismuth neodecanoate (as the first catalyst) of catalyst gross mass, is reacted.During the reaction, using gas phase color
Spectrometry judges reaction end, when the mass fraction of 6-caprolactone is 2%, it is believed that reaction terminates；And reaction product is cooled to
60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 5
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 3.3:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 120 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
0.05% dibutyl tin dilaurate (as the first catalyst) of agent gross mass, is reacted.During the reaction, make
Reaction end is judged with gas chromatography, when the mass fraction of 6-caprolactone is 2%, it is believed that reaction terminates；And reaction is produced
Object cools to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 6
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.4:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 150 DEG C, and it is mixed system and the first catalyst that quality, which is added,
1.2% zirconium-n-butylate (as the first catalyst) of gross mass, is reacted.During the reaction, using gas chromatography
Reaction end is judged, when the mass fraction of 6-caprolactone is 2.5%, it is believed that reaction terminates；And reaction product is cooled to 60
DEG C hereinafter, discharging save, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 7
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.3:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 155 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
0.15% bismuth neodecanoate of agent gross mass is urged (as the first catalyst), is reacted.During the reaction, using gas phase
Chromatography judges reaction end, when the mass fraction of 6-caprolactone is 0.5%, it is believed that reaction terminates；And reaction product is dropped
Temperature is to 60 DEG C hereinafter, discharging preservation, can be obtained trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester.
Embodiment 8
Present embodiments provide a kind of synthetic method of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester, the synthesis
Method includes:
6-caprolactone, the trihydroxyethyl isocyanuric ester that molar ratio is 2.5:1 are added into reactor, it is mixed to form first
Zoarium system.First mixed system is heated up to 100 DEG C, and in the case where vacuum degree is at least -0.095MPa, extracts the first mixed system
In moisture, wherein extract the time be 2 hours.Into reactor, feed flow is the nitrogen of 0.3L/min, so that the first mixing
System is in nitrogen atmosphere.First mixed system is heated to 120 DEG C, and it is that the first mixed system is urged with first that quality, which is added,
0.5% stannous octoate (as the first catalyst) of agent gross mass, is reacted.During the reaction, using gas phase color
Spectrometry judges reaction end, when the mass fraction of 6-caprolactone is 0.5%, it is believed that reaction terminates；And reaction product is cooled down
To 60 DEG C hereinafter, discharging saves, trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester can be obtained.
Embodiment 9
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 2:1 third
Olefin(e) acid forms the second mixed system.At 95 DEG C, it is that the second mixed system is urged with second that quality is added into the second mixed system
The trifluoromethane sulfonic acid (as the second catalyst) of agent gross mass 0.5% carries out the second reaction.During the reaction, it utilizes
High performance liquid chromatography judges reaction end, when total matter of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester and acrylic acid
When amount is the 15% of the preceding the two gross mass of reaction, it is believed that the second reaction terminates, at this time stopping heating.Hydrogen is added into reactor
Sodium hydroxide solution removes excessive acrylic acid and trifluoromethane sulfonic acid in reactor；Later, using in way of distillation removal reactor
Toluene remove remaining toluene using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass,
It can be obtained acrylate.
Embodiment 10
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 2.5:1's
Acrylic acid forms the second mixed system.At 120 DEG C, it is the second mixed system and that quality is added into the second mixed system
The methane sulfonic acid (as the second catalyst) of two catalyst gross masses 2% carries out the second reaction.During the reaction, height is utilized
Effect liquid phase chromatogram method judges reaction end, when the gross mass of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester and acrylic acid
For react before both gross mass 95% when, it is believed that second reaction terminate, at this time stop heating.Hydrogen-oxygen is added into reactor
Change sodium solution, removes excessive acrylic acid and methane sulfonic acid in reactor；Later, the first in way of distillation removal reactor is utilized
Benzene removes remaining toluene using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass
Obtain acrylate.
Embodiment 11
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 3.0:1's
Acrylic acid forms the second mixed system.At 80 DEG C, it is the second mixed system and second that quality is added into the second mixed system
The p-methyl benzenesulfonic acid (as the second catalyst) of catalyst gross mass 5% carries out the second reaction.During the reaction, height is utilized
Effect liquid phase chromatogram method judges reaction end, when the gross mass of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester and acrylic acid
For react before both gross mass 15% when, it is believed that second reaction terminate, at this time stop heating.Hydrogen-oxygen is added into reactor
Change sodium solution, removes excessive acrylic acid and methane sulfonic acid in reactor；Later, the first in way of distillation removal reactor is utilized
Benzene removes remaining toluene using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass
Obtain acrylate.
Embodiment 12
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 3.5:1's
Acrylic acid forms the second mixed system.At 105 DEG C, it is the second mixed system and that quality is added into the second mixed system
The trifluoromethane sulfonic acid (as the second catalyst) of two catalyst gross masses 1% carries out the second reaction.During the reaction, sharp
Reaction end is judged with high performance liquid chromatography, it is total when (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid
When quality is the 3% of the preceding the two gross mass of reaction, it is believed that the second reaction terminates, and stops heating at this time.It is added into reactor
Sodium hydroxide solution removes excessive acrylic acid and trifluoromethane sulfonic acid in reactor；Later, reactor is removed using the way of distillation
In toluene remove remaining first using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass
Benzene can be obtained acrylate.
Embodiment 13
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 4.0:1's
Acrylic acid forms the second mixed system.At 110 DEG C, it is the second mixed system and that quality is added into the second mixed system
The trifluoromethane sulfonic acid (as the second catalyst) of two catalyst gross masses 2% carries out the second reaction.During the reaction, sharp
Reaction end is judged with high performance liquid chromatography, it is total when (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid
When quality is the 0% of the preceding the two gross mass of reaction, it is believed that the second reaction terminates, and stops heating at this time.It is added into reactor
Sodium hydroxide solution removes excessive acrylic acid and trifluoromethane sulfonic acid in reactor；Later, reactor is removed using the way of distillation
In toluene remove remaining first using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass
Benzene can be obtained acrylate.
Embodiment 14
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 2.5:1's
Acrylic acid forms the second mixed system.At 90 DEG C, it is the second mixed system and second that quality is added into the second mixed system
The methane sulfonic acid (as the second catalyst) of catalyst gross mass 3% carries out the second reaction.During the reaction, using efficient
Liquid chromatography judges reaction end, when the gross mass of (the 6- hydroxyl 1- caproic acid) ester of trihydroxyethyl isocyanuric 3 and acrylic acid is
When reacting the 7% of both preceding gross mass, it is believed that the second reaction terminates, and stops heating at this time.Hydroxide is added into reactor
Sodium solution removes excessive acrylic acid and methane sulfonic acid in reactor；Later, the toluene in reactor is removed using the way of distillation,
After the quality of toluene is equal to the 10% of acrylate and toluene gross mass, remaining toluene is removed using stripper, can be obtained
Obtain acrylate.
Embodiment 15
Present embodiments provide a kind of synthetic method of acrylate, wherein the trihydroxyethyl isocyanide urine in the embodiment
Sour 3 (6- hydroxyl 1- caproic acid) esters are prepared by the synthetic method that embodiment 8 provides.
The synthetic method of the acrylate includes: to sequentially add into reactor and (the 6- hydroxyl of trihydroxyethyl isocyanuric 3
1- caproic acid) it ester toluene identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester is 3.0:1's
Acrylic acid forms the second mixed system.At 115 DEG C, it is the second mixed system and that quality is added into the second mixed system
The p-methyl benzenesulfonic acid (as the second catalyst) of two catalyst gross masses 3% carries out the second reaction.During the reaction, it utilizes
High performance liquid chromatography judges reaction end, when total matter of trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester and acrylic acid
When amount is the 10% of the preceding the two gross mass of reaction, it is believed that the second reaction terminates, at this time stopping heating.Hydrogen is added into reactor
Sodium hydroxide solution removes excessive acrylic acid and toluenesulfonic acid in reactor；Later, the first in way of distillation removal reactor is utilized
Benzene removes remaining toluene using stripper after the quality of toluene is equal to the 10% of acrylate and toluene gross mass
Obtain acrylate.
Reference examples 1
This reference examples provides a kind of acrylate, and the acrylate is by the trihydroxyethyl isocyanuric without any modification
Ester and acrylic acid are esterified and are prepared.Wherein, which buys from Sartomer Guangzhou Chemical Co., Ltd..
Reference examples 2
This reference examples provides a kind of acrylate, which is urinated by the trihydroxyethyl isocyanide after ethylene-oxide-modified
Acid esters and acrylic acid are esterified and are prepared.
Application Example
This application embodiment is to the water absorption rate of acrylate provided by embodiment 9, comparative example 1 and comparative example 2, elongation
Rate, modulus, curing rate, hardness and viscosity are tested one by one.
(1) water absorption rate
The acrylate that embodiment 9, comparative example 1 and comparative example 2 provide is filled in 5 having a size of 20mm one by one respectively
In the mold of × 20mm × 20mm, 15 samples are prepared altogether；And each sample is placed on UV (Ultra-Violet Ray, purple
Outside line) solidified in curing, taking-up is weighed respectively；At 25 DEG C, all samples are immersed in pure water, are taken afterwards for 24 hours
Out, and the moisture of each sample surfaces is dried, weighs again, calculates the water absorption rate of each sample.Its structure is as described in Table 1.
Table 1
(2) elongation, modulus
Firstly, 15 are prepared having a size of 80mm × 12mm × 12mm stretching sample, and the ingredient of every 5 samples is identical,
I.e. wherein 5 samples include following components in percentage by weight: acrylate 30%, polyether-polyurethane provided by embodiment 9
Acrylate 67%, photoinitiator 3%；Wherein 5 samples include following components in percentage by weight: provided by comparative example 9
Acrylate 30%, polyether urethane 67%, photoinitiator 3%；Other 5 samples include following weight percent
Component: acrylate 30%, polyether urethane 67% provided by comparative example 2, photoinitiator 3%.Then, sharp
The elongation and mold of each sample are tested with universal tensile instrument, result is as shown in table 2, table 3.
Table 2
Table 3
(3) curing rate
Firstly, 15 are prepared having a size of 80mm × 12mm × 12mm stretching sample, and the ingredient of every 5 samples is identical,
I.e. wherein 5 samples include following components in percentage by weight: acrylate 30%, polyether-polyurethane provided by embodiment 9
Acrylate 67%, photoinitiator 3%；Wherein 5 samples include following components in percentage by weight: provided by comparative example 9
Acrylate 30%, polyether urethane 67%, photoinitiator 3%；Other 5 samples include following weight percent
Component: acrylate 30%, polyether urethane 67% provided by comparative example 2, photoinitiator 3%.
Then, in 100mj/m2Energy under, above-mentioned 15 samples are solidified, and residual using infrared test double bond
Residual amount calculates each sample double bond conversion rate.Wherein, which characterizes above-mentioned 15 with the size of double bond conversion rate
The curing rate of sample；Double bond conversion rate is bigger, shows that curing rate is faster.Its test result is as shown in table 4.
Table 4
(4) hardness
Firstly, 15 are prepared having a size of 100mm × 100mm × 4mm stretching sample, and the ingredient of every 5 samples is identical,
I.e. wherein 5 samples include following components in percentage by weight: acrylate 30%, polyether-polyurethane provided by embodiment 9
Acrylate 67%, photoinitiator 3%；Wherein 5 samples include following components in percentage by weight: provided by comparative example 9
Acrylate 30%, polyether urethane 67%, photoinitiator 3%；Other 5 samples include following weight percent
Component: acrylate 30%, bisphenol A epoxy acrylate 67% provided by comparative example 2, photoinitiator 3%.Then, sharp
With the hardness of each sample of measuring pencil durometer, the results are shown in Table 5.
Table 5
(5) viscosity
At 25 DEG C using rotary viscometer to acrylate provided by embodiment 9, comparative example 1 and comparative example 2
Viscosity is tested one by one, and the results are shown in Table 6.
Table 6
In summary test result can be seen that the water absorption rate of acrylate provided by embodiment 9 and comparative example 1 is mentioned
The water absorption rate of the acrylate of confession is not much different, but the water absorption rate of acrylate provided by comparative example 2 is too big；It is embodiment 9, right
Ratio 1 and the elongation of comparative example 2 are almost the same, but the modulus of 9 acrylate of embodiment is substantially reduced, and expand of the invention real
Application of the olefin(e) acid ester of example offer in flexible paint is provided；It is real in the hardness test of embodiment 9, comparative example 1 and comparative example 2
Apply that example 9 is consistent with the hardness of comparative example 1, the hardness of comparative example 2 is obviously relatively low；In terms of curing rate, the solidification speed of embodiment 9
Degree is most fast, and the curing rate of comparative example 2 is obviously relatively low；In terms of viscosity, the viscosity and comparative example 2 of embodiment 9 are close, and compare
The viscosity of example 1 is obviously bigger than normal.
As it can be seen that the obtained acrylate of the synthetic method provided through the embodiment of the present invention not only water-tolerant, solidification
Speed is fast, hardness is big, and modulus is small, can be applied in flexible paint, expand application range.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (15)
1. a kind of synthetic method of acrylate, which is characterized in that the synthetic method includes:
It is (2~4) that molar ratio is added into reactor: 1 6-caprolactone, trihydroxyethyl isocyanuric ester form the first mixing
System, and remove the moisture in first mixed system；
Under nitrogen atmosphere, first mixed system is heated to 100 DEG C~180 DEG C, and into first mixed system
The first catalyst is added, carries out the first reaction, obtains trihydroxyethyl isocyanuric 3 (6- hydroxyl 1- caproic acid) ester；Described first urges
The quality of agent is the 0.01%~2% of first mixed system and the first catalyst gross mass；
After reaction to described first, it is sequentially added in Xiang Suoshu reactor and 3 (the 6- hydroxyl of trihydroxyethyl isocyanuric
1- caproic acid) ester solvent identical in quality, with the molar ratio of trihydroxyethyl isocyanuric 3 (the 6- hydroxyl 1- caproic acid) ester be (2~
4): 1 acrylic acid forms the second mixed system；
At 80 DEG C~120 DEG C, the second catalyst is added in the second mixed system of Xiang Suoshu, carries out the second reaction, obtains propylene
Acid esters；The quality of second catalyst be second mixed system and the second catalyst gross mass 0.5%~
5%.
2. synthetic method according to claim 1, which is characterized in that the 6-caprolactone and the trihydroxyethyl isocyanide are urinated
The molar ratio of acid esters is (2.5~3.5): 1.
3. synthetic method according to claim 1, which is characterized in that the water in the first mixed system of the removal
Point, comprising:
First mixed system is heated to 80 DEG C~110 DEG C, and in the case where vacuum degree is at least -0.095MPa, described in extraction
Moisture in first mixed system, until the quality of the moisture is less than the 0.05% of the first mixed system quality.
4. synthetic method according to claim 1, which is characterized in that the moisture in removal first mixed system
Afterwards, feed flow is at least the nitrogen of 0.1L/min in Xiang Suoshu reactor, so that first mixed system is in the nitrogen
During atmosphere is enclosed.
5. synthetic method according to claim 1, which is characterized in that the quality of first catalyst is described first mixed
Zoarium system and the 0.05%~1% of the first catalyst gross mass.
6. synthetic method according to claim 1, which is characterized in that first catalyst is stannous octoate, two laurels
At least one of sour dibutyl tin, zirconium-n-butylate, bismuth neodecanoate.
7. synthetic method according to claim 1, which is characterized in that by first mixed system be heated to 130 DEG C~
After 140 DEG C, first catalyst is added in Xiang Suoshu reactor.
8. synthetic method according to claim 1, which is characterized in that in carrying out first reaction process, using gas
Phase chromatography obtains mass fraction of the 6-caprolactone in the reactor, if the mass fraction is equal to or less than 5%
When, determine that first reaction terminates.
9. synthetic method according to claim 1, which is characterized in that the solvent is toluene.
10. synthetic method according to claim 1, which is characterized in that the acrylic acid and the trihydroxyethyl isocyanide are urinated
The molar ratio of sour 3 (6- hydroxyl 1- caproic acid) esters is (2.7~3.7): 1.
11. synthetic method according to claim 1, which is characterized in that second catalyst is methane sulfonic acid, to toluene
At least one of sulfonic acid, trifluoromethane sulfonic acid.
12. synthetic method according to claim 1, which is characterized in that the quality of second catalyst is described second
The 1%~4% of mixed system and the second catalyst gross mass.
13. synthetic method according to claim 1, which is characterized in that described molten being sequentially added into the reactor
After agent, the acrylic acid, and at 90 DEG C~110 DEG C, it is added second catalyst in Xiang Suoshu reactor, carries out described the
Two reactions.
14. a kind of acrylate is prepared, the acrylate using the described in any item synthetic methods of claim 1-13
Chemical structural formula it is as follows:
15. a kind of coating, which is characterized in that the coating includes acrylate described in claim 14.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
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| CN104418815A (en) * | 2013-09-05 | 2015-03-18 | 安庆飞凯高分子材料有限公司 | Preparation method of tri(2-ethoxy) isocyanurate acrylate mixture |
| JP2015101606A (en) * | 2013-11-21 | 2015-06-04 | 関西ペイント株式会社 | Coating composition and coated article |
| CN105348208A (en) * | 2015-12-11 | 2016-02-24 | 安庆飞凯高分子材料有限公司 | Preparation method of tris(2-hydroxycyclohexyl) isocyanuric acid triacrylate |
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| JPS6154788B2 (en) * | 1983-10-17 | 1986-11-25 | Toa Gosei Chem Ind | |
| CN104418815A (en) * | 2013-09-05 | 2015-03-18 | 安庆飞凯高分子材料有限公司 | Preparation method of tri(2-ethoxy) isocyanurate acrylate mixture |
| JP2015101606A (en) * | 2013-11-21 | 2015-06-04 | 関西ペイント株式会社 | Coating composition and coated article |
| CN105348208A (en) * | 2015-12-11 | 2016-02-24 | 安庆飞凯高分子材料有限公司 | Preparation method of tris(2-hydroxycyclohexyl) isocyanuric acid triacrylate |
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| CN115260112A (en) * | 2022-06-27 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Sexek derivative and preparation method and application thereof |
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Application publication date: 20190524 |